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Dicyclopalladated Complexes of Asymmetrically Substituted Azobenzenes: Synthesis, Kinetics and Mechanisms


Juribašić, Marina; Budimir, Ana; Kazazić, Snježana; Ćurić, Manda
Dicyclopalladated Complexes of Asymmetrically Substituted Azobenzenes: Synthesis, Kinetics and Mechanisms // Inorganic chemistry, 52 (2013), 21; 12749-12757 doi:10.1021/ic402017v (međunarodna recenzija, članak, znanstveni)


Naslov
Dicyclopalladated Complexes of Asymmetrically Substituted Azobenzenes: Synthesis, Kinetics and Mechanisms

Autori
Juribašić, Marina ; Budimir, Ana ; Kazazić, Snježana ; Ćurić, Manda

Izvornik
Inorganic chemistry (0020-1669) 52 (2013), 21; 12749-12757

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
Azobenzenes; dicyclopalladation; kinetics; mechanism; DFT

Sažetak
Two series of new dicyclopalladated complexes {; ; ; (DMF)PdCl(mu-R1C6H3N=NC6H3R2)PdCl(DMF)}; ; ; of 4, 4’-functionalized azobenzenes with substituents of varying electron-donating or electron-withdrawing strength (R1=H, NMe2 ; R2=H, Cl, Br, I, OMe, PhNH, CO2H, SO3Na, NO2) have been synthesized and fully characterized. 1H NMR spectroscopy along with the ESI mass spectrometry unambiguously identified the new complexes in the solution and their solid-state structures were determined by X-ray crystallography. The presence of easily exchangeable solvent ligands was confirmed by 1H NMR spectroscopy, X-ray experiments and ESI mass spectrometry. The complexes were additionally characterized by UV-vis and fluorescence spectroscopies. The effect of different 4, 4’-substituents on the formation rate of mono- and dicyclopalladated azobenzenes was studied by the UV-vis spectroscopy. The experimental results are complemented by the quantum-chemical (DFT) calculations in order to rationalize the kinetic results as well as substituent effects on the reaction rates. It was found that the mono- and dicyclopalladation reactions of azobenzenes proceed in two consecutive processes, adduct formation and palladation step. The rate-determining step in both palladations is the breaking of the ortho C–H bond that has been confirmed as an electrophilic substitution process by Hammett correlations and DFT calculations.

Izvorni jezik
Engleski

Znanstvena područja
Kemija



POVEZANOST RADA


Projekt / tema
006-0061247-0009 - Kinetika i mehanizam katalitičkog antioksidacijskog djelovanja Mn-porfirina (Ana Budimir, )
098-0982915-2945 - Spektroskopija, kemijska svojstva i reakcije biološki aktivnih molekula (Branka Kovač, )
098-0982915-2950 - Dizajn, sinteza i svojstva organskih liganada i njihovih metalnih kompleksa (Manda Ćurić, )

Ustanove
Farmaceutsko-biokemijski fakultet, Zagreb,
Institut "Ruđer Bošković", Zagreb

Časopis indeksira:


  • Current Contents Connect (CCC)
  • Web of Science Core Collection (WoSCC)
    • Science Citation Index Expanded (SCI-EXP)
    • SCI-EXP, SSCI i/ili A&HCI
  • Scopus
  • MEDLINE


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